Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.
MINISTRY OF EDUCATION AND TRAINING HA NOI NATIONAL UNIVERSITY OF EDUCATION - PHAM VAN THONG STUDY ON SYNTHESIS, STRUCTURE AND PROPERTIES OF SOME ORGANOPLATINUM(II) COMPLEXES BEARING ISOPROPYL EUGENOXYACETATE Specialized: Inorganic chemistry Code: 9.44.01.13 SUMMARY OF THESIS DOCTOR OF PHYLOSOPHY IN CHEMISTRY HANOI, 2023 The thesis has been completed at HANOI NATIONAL UNIVESITY OF EDUCATION Supervisor: Assoc Prof Dr Nguyen Thi Thanh Chi (Hanoi National University of Education) Assoc Prof Dr Huynh Han Vinh (National University of Singapore) Reviewer 1: Assoc Prof Dr Duong Ba Vu HCMC University of Education Reviewer 2: Assoc Prof Dr Nguyen Hung Huy VNU University of Science Reviewer 3: Assoc Prof Dr Le Thi Hong Hai Hanoi National University of Education The thesis will be defended in front of the University-level thesis evaluation committee at Hanoi National University of Education ……………… 2023 The thesis can be found at: National Library, Hanoi or Library of Hanoi National University of Education PUBLISHED IN THE THESIS CONTENT Pham Van Thong, Luc Van Meervelt, Nguyen Thi Thanh Chi* Cyclometalated platinum(II) complexes bearing natural arylolefin and quinolines ligands: Synthesis, characterizations, and in vitro cytotoxicity, Polyhedron, 228, 116160, (2022, Q2) Nguyen Thi Thanh Chi*, Pham Van Thong, Ngo Tuan Cuong, Luc Van Meervelt * Reaction pathways of the diplatinum complexes bearing a phenylpropene derived π/σ-chelator [Pt(µ-Cl)(arylolefin)]2 with weak/strong σ-donor neutral ligands, ChemistrySelect, (2022, Q2) (excepted) Pham Van Thong, Nguyen Thi Thanh Chi*, Mohammad Azam*, Cu Hong Hanh, Le Thi Hong Hai, Le Thi Duyen, Saud I Al-Resayes, Mahboob Alam, Nguyen Van Hai NMR investigations on a series of diplatinum(II) complexes possessing phenylpropenoids in CDCl and CD3CN: Crystal structure of a mononuclear platinum complex, Polyhedron, 115612, (2022, Q2) Nguyen Thi Thanh Chi*, Van Thong Pham, Han Vinh Huynh* Mixed Arylolefin/NHC Complexes of Platinum(II): Syntheses, Characterizations and In-Vitro Cytotoxicities, Organometallics, 39(19), 3505– 3513 (2020, Q1) Nguyen Thi Thanh Chi, Pham Van Thong and Luc Van Meervelt * Crystal structures of three platinacyclic complexes bearing isopropyl eugenoxyacetate and pyridine derivatives, Acta Cryst., E76, 1012–1017 (2020, Q3) Pham Van Thong, Nguyen Manh Thang, Nguyen Thi Thanh Chi * Study on the interaction between [Pt(µ-Cl)(isopropyl eugenoxyacetate-1H)]2 and 1,3-diisopropylbenzimidazolium bromide, V J Chem., 57(2), 218-224 (2019) Nguyen Thi Thanh Chi*, Pham Van Thong, Truong Thi Cam Mai, Luc Van Meervelt* Mixed natural arylolefin– quinoline platinum(II) complexes: synthesis, structural characterization and in vitro cytotoxicity studies, Acta Cryst., C74, 1732-1743 (2018, Q1) Han Vinh Huynh*, Van Thong Pham, Nguyen Thi Thanh Chi* Cyclometallated Platinum(II) Complexes with a Phenylpropene-derived π/σ-Chelator and N-heterocyclic Carbenes, Eur J Inorg Chem., 48, 56505655 (2017, Q1) Pham Van Thong, Nguyen Hien, Nguyen Son Ha, Nguyen Thi Thanh Chi * Synthesis and structure of some azolium salt, V J Chem., 55(2), 249-254 (2017) 10 Pham Van Thong, Truong Thi Cam Mai, Nguyen Thi Thanh Chi* The interaction between K[PtCl3(isopropyl eugenoxyacetate)] and two pyridine’s derivatives, Journal of Science of HNUE, 62, 18-25 (2017) 11 Chi Nguyen Thi Thanh, Thong Pham Van, Hai Le Thi Hong, Luc Van Meervelt* Crystallization experiments with the dinuclear chelate ring complex di-μ-chlorido-bis(η2-2-allyl-4-methoxy-5-{[(propan-2yloxy)carbonyl]methoxy}-phenyl-κCC1)platinum(II), Acta Cryst., C72, 758-764 (2016, Q1) 12 Phạm Văn Thống, Nguyễn Thị Thanh Chi* Nghiên cứu tổng hợp cấu trúc hai phức chất K[PtCl3(isopropyl eugenoxyacetate)] [PtCl(isopropyl eugenoxyacxetate-1H)] 2, Tạp chí Hóa học, 52(3), 381-386 (2014) OTHER RELATED PUBLICATIONS Pham Van Thong, Do Thi Thom, Nguyen Thi Thanh Chi * Synthesis and structure of two platinum(II) complexes bearing N-heterocyclic carbenes and dimethyl sulfoxide, V J Chem., 56(2), 146-151 (2018) Chi Nguyen Thi Thanh*, Mai Truong Thi Cam, Thong Pham Van, Long Nguyen, My Nguyen Ha, Luc Van Meervelt* Synthesis, structure and in vitro cytotoxicity of some platinum(II) complexes containing eugenol and 8-hydroxyquinoline-derived chelator, Acta Cryst., C73, 1030-1037 (2017) Phạm Văn Thống, Trương Thị Cẩm Mai, Bạch Thị Mãi, Nguyễn Thị Thanh Chi * Tổng hợp, cấu trúc, tính chất hai phức chất khép vịng platinum(II) chứa methyleugenol quinaldic acid, Tạp chí Hóa học, 54(5e1,2), 154-159 (2016) Phạm Văn Thống, Hoàng Văn Trường, Lê Thị Duyên, Nguyễn Thị Thanh Chi* Phản ứng bất thường potasium tricloropiperidinplatinat(II) với para-nitroaniline, Tạp chí Hóa học, 53(3e12), 468-472 (2015) Chi Nguyen Thi Thanh, Truong Hoang Van, Thong Pham Van, Ngan Nguyen Bich and Luc Van Meervelt* Crystal structure of trans-dichlorido(4-nitroaniline-κCN)(piperidine κCN)platinum(II), Acta Cryst., E71, 644-646 (2015) Nguyễn Thị Thanh Chi*, Phạm Văn Thống, Trần Thị Đà Nghiên cứu tổng hợp, cấu trúc phức chất khép vịng platinum(II) chứa eugenoxyacetic acid, Tạp chí Hóa học, 52(5A), 319-323 (2014) Nguyễn Thị Thanh Chi*, Phạm Văn Thống Tổng hợp, cấu trúc hoạt tính kháng tế bào ung thư phức chất cis-[PtCl2(piperidine)(p-cloaniline)] cis-[PtCl2(piperidine)(xyclohexylamine)], Tạp chí Khoa học ĐHSPHN, 59(1), 156-161 (2014) 1 INTRODUCTION Reasons for choosing the topic The platinum(II) complexes have had an enormous role not only in theory but also in practical applications, especially in medical practices and in the organic synthesis industry In the medical field, there have been three generations of platinum complexes which are widely used in human cancer treatment in the names of Cisplatin, Carboplatin and Oxaliplatin However, due to their disadvantage of high toxicity and not responding to the rise of different types of cancer, research on synthesis of new platinum(II) complexes, especially complexes containing natural ligands, is attracting the attention of many domestic and foreign scientists In the chemical industry, catalysts are used to manufacture 80% of chemical products, particularly organometallic compounds for numerous processes Their importance is highlighted in Nobel prizes, such as Nobel Prize for organomagnesium compound of Grignard (1912); Nobel Prize for olefin metathesis with carbene organic catalyst by Y Chauvin , R H Schrock (2005); for palladium-catalyzed cross-coupling by Richard F Heck, Ei-ichi Negishi, Akira Suzuki (2010), etc Platinum is known to be a precursor that creates catalysts for many important metabolic processes such as hydrosilylation reactions, hydroaminations, C-C coupling reaction In those processes, platinum complexes act as active intermediates In Vietnam, research on organometallic platinum complexes has only started in the first decade of the 21st century, putting it two centuries behind research conducted elsewhere in the world However, the complex research group at Hanoi National University of Education has synthesized organoplatinum complexes with interesting structure Using simple and popular reagents, the authors have initiated a method for the synthesis of dinuclear chelate ring platinum complexes with general formula [Pt(μ-Cl)(arylolefin)]2, in which arylolefin is extracted or synthesized from vegetable essential oils such as safrole, methyleugenol, alkyl eugenoxyacetate These dinuclear complexes have been studied to interact with different amines to obtain mononuclear platinum complexes Most of the collected complexes that were tested for inhibitory activity of human cancer cells have demonstrated promising results (Fig 1) However, these complexes contain arylolefin ligand, which is isopropyl eugenoxyacetate This substance has not been used widely, and so far there has been no research on converting these dinuclear chilate ring complexes into new compounds for the purpose of creating catalysts R R Cl Cl amine Pt R Pt amine O amine Pt Cl Pt N R Fig Synthesis of some platinum(II) bearing arylolefin complexes Continuing the research on the Pt(II) bearing arylolefin complexes in this topic, we chose the arylolefin isopropyl eugenoxyacetate - a derivative of eugenol (accounting for 70% in clove basil oil) as the research object for its applicability in medicine and organic synthesis catalysis In this study focus on the following tasks: - Synthesizing isopropyl eugenoxyacetate (iPrEugH) from clove basil oil and some azolium chloride salts from nitrogen heterocyclic azoles - From Pt and other chemicals, synthesizing complex K[PtCl3(iPrEugH)] (1) - From complex 1, synthesizing a dinuclear chelate ring complex containing iPrEug with the formula [Pt(μ-Cl)(iPrEug)]2 (2) and determining its structure by single crystal X-ray diffraction - Studying the interaction of complex with heterocyclic bidentate amines - Studying the interaction of complex with tricyclohexylphosphine and triphenylphosphine - Studying the interaction of complex with the synthesized azolium chloride salts to formPt(II) complexes containing simultaneously iPrEug and Nheterocyclic carbene (NHC) - Using chemical, physicochemical and physical methods to determine the composition and structure of the obtained complexes - Investigating the inhibitory activity on cancer cells of some complexes containing olefins and amines and initially studying the catalytic activities of some complexes for Sonogashira and hydrosilylation reactions New contributions of the thesis From mononuclear complex K[PtCl3(iPrEugH)] (1), a new dinuclear chelate complex of [Pt(μ-Cl)(iPrEug)]2 (2) has been synthesized, which is perceived as the crucial component leading to synthesis directions of other chelate organometallic compound of Pt(II) bearing iPrEug Three-dimensional structure of complex was determined and characterized using single crystal Xray diffraction (XRD), which is the basis for explaining other interesting results Efficient reacting conditions were found to prepare a series of new 20 mononuclear complexes containing iPrEug and coordinating sovent, amine, phosphine, or nitrogen heterocyclic carbene, including [PtX(iPrEug)L] (3–5, 10–14, 17–22); [Pt(iPrEug)L] (6–9); [PtCl(iPrEug)(PR3)] (15, 16), all of which come from dinuclear complex Structures of these complexes were determined through the combination of various up-to-date characterization techniques With detailed analysis on NMR and XRD results, not only their complicated structures were justified, but also some conclusions were drawn with predictive analytics on mechanisms of substitution reactions of dinuclear complexes [Pt(μ-Cl) (arylolefin)]2 with other ligands In addition, the predictive analytics can help with determining the cis/trans configuration of the obtained products from these reactions The cytotoxicity test results of the four complexes containing amine groups on four human cancer cell lines have shown that complex 10 (very soluble in water) had inhibitory effects on the growth of all tested cell lines, with the obtained IC50 values ranging from 4.03–7.07 µM (which are greatly lower than those values of cisplatin) These data established the need to further investigate the complex 10 for its potential in biomedical applications The initial analysis on the catalytic activities of compounds 17–19 for the hydrosilylation reaction of silane derivatives and phenylacetylene showed that after hours of reacting at 700C, in the air, these compounds exhibited a great catalytic rate at 0.5 mol% The catalytic mechanism of 17–19 for these reactions was initially proposed This positive result has proven a promising application in the field of organic synthesis catalysis at industrial scale Layout of the thesis The thesis consists of three parts: the main content (113 pages), references (14 pages) and the appendix (102 pages) Specifically: - The main content of the thesis includes: pages of introduction, 24 overview pages, 16 experimental pages, 66 results and discussion pages, conclusion pages and pages of the author's portfolio This entire section has 54 pictures and 23 tables - References: 145 documents including 12 Vietnamese and 133 English documents - The appendix of the thesis includes: Spectrometer to determine the structural composition and attribution results of the studied compounds, results of resistance testing of cancer cells and catalyst test MAIN CONTENT OF THESIS CHAPTER OVERVIEW Overview of synthesis and properties of research ligands for complexation (alkyl eugenoxyacetate, phopshine and N-heterocyclic carbene - NHC, heterocyclic bidentate amines); research situation of platinum(II) complexes containing olefin, phosphine and NHC ligands; antitumor activity and catalytic activity of platinum(II) complexes CHAPTER EXPERIMENTAL 2.1 Chemicals, apparatus and research equipment 2.2 Synthesis of ligands 2.2.1 Synthesis of isopropyl eugenoxyacetate (iPrEugH) The iPrEugH ligand was synthesized by reaction of eugenoxyacetic acid with propan-2-ol for 18 hours at 100oC, using sulfuric acid as catalyst, the yield was 45% 2.2.2 Synthesis of azolium chloride salts The azolium chloride salts are synthesized by alkylation of imidazoles, benzimidazoles and triazoles with benzyl chloride or 2-bromopropane The reactions were carried out in CH3CN solvent at 80−85oC, after 48 hours, the products were obtained with a yield of 75−80% NaOH/CH3CN N BnCl X N N X N H K2CO3/CH3CN i Cl N PrBr X C: Bn2-imy·HCl Bn2-bimy·HCl N: Bn2-tazy·HCl N N BnCl CH3CN Cl N i Pr,Bn-bimy·HCl Fig 2.1 Diagram of the synthesis azolium chlorides 2.3 Synthesis of complexes The complexes were synthesized with the following procedure in Figure 2.2 Pt HNO3/HCl/NaCl C2H5OH/KCl K[PtCl3(C2H4)].H2O i PrEugH K[PtCl3(iPrEugH)] (1) [PtCl(iPrEug)(Sol)] (3–5) Sol acetone-H2O [PtCl(iPrEug)]2 PR3 (N,OH) i (2) [PtCl( PrEug)(N,O)] (6–9) NHC·HCl Ag2O/Na2CO3 amine [PtCl(iPrEug)(amine)] (10–13) [PtCl(iPrEug)(NHC)] (17–20) MX [PtCl(iPrEug)(PCy3)] (14) [PtCl(iPrEug)(PR3)2] (15, 16) [PtX(iPrEug)(NHC)] (21, 22) Fig 2.2 Synthetic scheme of the examined complexes Where: - Sol (solvent): MeCN (3), Me2SO (4), Me2NCHO (5) - (N,OH): quinoline-8-ol (6), 2-methylquinoline-8-ol (7), 5,7dichloroquinoline-8-ol (8), quinoline-2-carboxylic acid (9) - Amine: 1,10-phenanthroline (10), 2,2’-bipyridine (11), 4,4’-dimethyl-2,2’bipyridine (12), 6,6’-dimethyl-2,2’-bipyridine (13) - PR3: tricyclohexylphosphine (14, 15), triphenylphosphine (16) NHC·HCl: 1,3-dibenzylimidazolium chloride (17) 1,3dibenzylbenzimidazolium chloride (18), 1,3-dibenzyl-1,2,4-triazolium chloride (19), 1-benzyl-3-isopropylbenzimidazolium chloride (20) - MX: LiBr (21), KI (22) 2.3.1 Synthesis of K[PtCl3(iPrEugH)] (1) The complex K[PtCl3(iPrEugH)] was synthesized from Zeise’s salt and i PrEugH with the yield of 95%according to the following reaction: K[PtCl3(C2H4)] + iPrEugH → K[PtCl3(iPrEugH)] + C2H4 2.3.2 Study on the synthesis of [Pt(μ-Cl)(iPrEug)]2 (2) The complex [Pt(μ-Cl)(iPrEug)]2 was synthesized from Zeise’s salt and i PrEugH with the yield of 70% in the solvent mixture of acetone-water (1 : 10, v/v) at 60 oC for 7hours The reaction equation is as indicated below: 2K[PtCl3(iPrEugH)] [Pt(μ-Cl)(iPrEug)]2 + 2KCl + 2HCl Producing a single crystals of the complex [Pt(μ-Cl)(μ-Cl)(Cl)(μ-Cl)(iPrEug)]2 Solvent vapor diffusion method: In the solvent system of chloroform/diethyl ether or dichloromethane/diethyl ether, the greenish yellow needle crystals were obtained The product is complex Solvent evaporation method: In the solvents such as acetonitrile, dimethyl sulfoxide and dimethyl formamide, the obtained crystals are different from so these complexes are denoted as 3, and 2.3.3 Study on the interaction of [Pt(µ-Cl)(iPrEug)]2 with heterocyclic bidentate amines The complex reacts with amines with formula (N,OH) to form complexes 6-9 as the following equation: [Pt(μ-Cl)(iPrEug)]2 + 2(N,OH) → 2[Pt(iPrEug)(N,O)] + 2HCl While using the amine 1,10-phenalthroline and the derivative of 2,2'bipyridine, complexes 10–13 are obtained The reactions take place according to the equation: [Pt(μ-Cl)(iPrEug)]2 + amine → 2[PtCl(iPrEug)(amine)] The reactions were carried out in acetone or acetone/water solvents at room temperature Single crystals of complexes 7, 9–11, 13 were grown by solvent evaporation or solvent vapor diffusion 2.3.4 Study on the interaction of [Pt(µ-Cl)(iPrEug)]2 with derivatives of phosphine We changed a number of reaction conditions when studying the interaction of with phosphine derivatives, including solvent, conductive operation, and the : PR3 molar ratio The results show that the reaction can occur as the equation: [Pt(μ-Cl)(iPrEug)]2 + PR3 → 2[PtCl(iPrEug)(PR3)] [Pt(μ-Cl)(iPrEug)]2 + PR3 → 2[PtCl(iPrEug)(PR3)2] Through the purification process, three clean complexes, 14–16, are obtained with an efficiency of 90-93% Single crystals of 14 and 16 were grown by solvent evaporation 2.3.5 Study on the interaction of [Pt(μ-Cl)(iPrEug)]2 with azolium chloride salts The synthesis of 17–20 was carried out in acetone at room temperature in the presence of Ag2O or Na2CO3 After hours of reaction, the product was obtained with the yield of 85–90% The reaction takes place according to the equation: [Pt(μ-Cl)(iPrEug)]2 + 2(NHC·HCl)→ 2[PtCl(iPrEug)(NHC)] (17–20) Complexes 21 and 22 were synthesized according to the equation: [PtCl(iPrEug)(NHC)] + MX → [PtCl(iPrEug)(NHC)] Single crystals of 18, 20–22 were grown by solvent evaporation 2.4 STUDY ON THE COMPONENT AND STRUCTURE OF OBTAINED PRODUCTS 2.4.1 Study on the components Thin layer chromatography method The products were tested for purity by chromatography on silufol-UV thin plate, showing traces by UV lamp at the wavelength of 254nm at the Department of Chemistry, Hanoi National University of Education (HNUE) Determination of water of crystallization proportion and platinum The water of crystallization proportion and platinum of the complexes 1, 2, 14–16, 20 and 22 were determined by weight method at the Department of Chemistry, Faculty of Chemistry, HNUE Molecular electrical conductivity measurement Molecular electrical conductivity of 10–12 was measured on Conductivity Meter Hach - 88119 N at the Department of Chemistry, HNUE Atom technical analysis method Atom technical analysis of complexes 17–19 and 21 were measured on the Perkin-Elmer PE 2400 engine at the Department of Chemistry, National University of Singapore The ESI MS spectroscopy The ESI-MS spectrum was recorded on a 1100 LC-MSD-Trap-SL engine at Institute of Chemistry, Vietnam Academy of Science and Technology 2.4.2 Study on the structures Infrared spectroscopy (μ-Cl)(IR) The infrared spectrum was recorded on IMPACK-410 NICOLET spectrometer, at Institute of Chemistry, Vietnam Academy of Science and Technology and the Department of Chemistry, HNUE Nuclear magnetic resonance spectrocopy (μ-Cl)(NMR) Nuclear magnetic resonance spectrum of 1H NMR was recorded on Bruker AVANCE III (500 MHz) in suitable solvent at Institute of Chemistry, Vietnam National Academy of Science and Technology and the Department of Chemistry, VNU Hanoi-University of Science Single crystal X-Cl)(ray diffraction method Single crystal X-ray diffraction of 2, 3, 7–10, 13, 14, 16, were measured on Bruker SMART 6000 at 100K at KU Leuven, Kingdom of Belgium, of 18, 19– 21 were measured on Bruker AXS SMART APEX at the Department of Chemistry, National University of Singapore 2.5 COMPLEXES BIOLOGICAL AND CATALYTIC ACTIVITIES EXAMINATION 2.5.1 Complexes anticancer activities examination The complexes 6, 7, 10, 11 and cisplatin were tested for the anticancer activity at Applied Biochemistry Department, Institute of Chemistry, Vietnam Academy of Science and Technology on human cancer cell lines: KB, HepG2, LU-1 and MCF7 2.5.2 Complexes catalytic activities examination The complexes 17–19 were tested for the catalytic activity for types of reactions: Sonogashira between phenylacetylene and 4-bromobenzaldehyde and hydrosilylation between derivatives of silane and phenylacetylene Catalytic activity of Sonogashira reaction examination A mixture of 4-bromobenzaldehyde (1.0 mmol), phenylacetylene (1.2 mmol) and 18 (5 mol%) in triethylamine (3 mL) was degassed by Ar followed by stirring at different temperatures and times After stopping the reaction, the mixture was added with water and was extracted with diethyl ether The removal of diethyl ether occcurred under reduced pressure to yield a white solid The product was measured and analysed 1H NMR spectra but no desired product was obtained Catalytic activity of hydrosilylation reaction examination 10 OR H3CO Cl Pt1 Sol Pt2 Cl OR O O OR Cl Pt N OCH3 RO (2) R: CH2COOCH(CH3)2 OR Cl Pt O S (3) Cl O (4) Pt O N (5) Fig 3.13 Diagram of synthesizing reaction of [PtCl(iPrEug)(solvent)] (3−5) 3.2 STUDY ON THE INTERACTION BETWEEN [Pt(μ-Cl)(iPrEug)]2 WITH BIDENTATE AMINES AND DETERMINATION OF COMPONENT AND STRUCTURE OF OBTAINED COMPLEXES 3.2.1 Study on the interaction between [Pt(μ-Cl)(iPrEug)]2 with bidentate amines When complex reacts with RQOH-type amines, we obtain neutral complexes 6−9 with high efficiency 85 ÷ 93%, the structure was shown in Fig 3.14 The obtained complexes is square planar, heteroatom N is at the cis position compared to the allyl group in the coordination sphere H3CO OCH2COOCH(CH3)2 H3CO OH Cl2 Pt OCH2COOCH(CH3)2 Pt O + 2 N Cl1 OCH3 (H3C)2HCOOCH2CO + HCl Pt N OH : quinolin-8-ol (6); 2-methylquinolin-8-ol (7); 5,7-dichloroquinolin-8-ol (8) quinoline-2-carboxylic acid (9) N Fig 3.14 Synthesizing reaction equation of [Pt(iPrEug)(amine)] (6−9) With 1,10-phenalthroline and a derivative of bipyridine, when they react with at the molar ratio of 2: amine, which is 1: 2, we get product 10−13 with high efficiency (90 ÷ 95%) From the results of the molecular electrical conductivity measurement, the ESI-MS, IR and 1H NMR spectra, it can be predicted that they exist in ion structure A or neutral structure B as shown in Fig 3.15 H3CO OCH2COOCH(CH3)2 N OCH2COOCH(CH3)2 Cl N Pt Pt (A) H3CO N (B) Cl N Fig 3.15 The expected structure of 10−13 XRD results show that 10−13 has B structure, which means Pt(II) represents the coordinate number This is an abnormal phenomenon in the Pt(II) complex system containing arylolefin and amine The cause of this 11 phenomenon may be due to the presence of the σ, π-donor/π-acceptor bond and the chelate ring coordination of the strong ligand (N,N-chelate) as well as the phenyl group in 10 −13 3.2.2 Determination of component and structure of obtained complexes From the results of analysing ESI-MS, IR, 1H NMR and XRD spectra, the structure of complexes are determined and presented in Figures 3.15, 3.23, 3.24 and in the diagram in 3.14 Some data of ESI-MS, NMR and XRD spectra of complexes were listed in Table 3.5-3.9 Table 3.5 Some detected ions on ESI-MS spectra of 6−13, m/z (au), % Complex 10 11 12 13 [M + H]+ [M + H - C3H6]+ 603 (100) 561 (10) 617 (100) 574 (15) 671 (25) 596 (30) 631 (100) 589 (30) - [M + Cl]- [M - amine + 2Cl]- [M - Cl]+ 637 (25) 529 (100) 650 (100) 529 (50) 706 (100) 529 (100) 666 (100) 638 (100) 614 (100) 642 (100) 642 (10) Table 3.6 1H NMR signals of iPrEug in and 6−13, (ppm), J (Hz) O H9 O O O H10cis 10 Pt H tr ans O N (6-9) Complex (c) * H8a 2,59/2,57 d JPtH 110 (a) 2,85 d (a) 2,78 d (a) 2,70 ov (c) 10 (b) 11 (b) 12 (b) 13 (c) 2,86 d JPtH 100 3,16 d JPtH 100 3,09 d JPtH 100 2,43 d JPtH 100 2,43 d JPtH 100 H8b O H9 O O O N H10cis 10 H Pt trans N Cl (10-13) H9 H10cis H10trans H3 H6 5,08 m 4,29/4,26 d 4,01 d 3,77 ov 6,57 s 6,40/6,38 s 2 JPtH 70 JPtH 70 JPtH 70 4,89 m 4,25 d 7,09 s 3,64 ov 3,68 d 6,73 s JPtH 60 JPtH 60 JPtH 40 4,51 d 3,60 d 7,20 s 3,66 ov 5,08 m 6,74 s 2 JPtH 60 JPtH 60 JPtH 40 4,87 m 4,22 d 3,69 d 6,98 s 3,53 dd 6,60 s 2 JPtH 70 JPtH 70 JPtH 70 JPtH 40 5,53 m 4,63 d 4,02 d 7,02 s 4,05 dd 6,68 s 2 JPtH 60 JPtH 60 JPtH 60 JPtH 40 5,99 m 4,69 d 4,41 d 6,93 s 4,04 dd 6,98 s 2 JPtH 70 JPtH 60 JPtH 60 JPtH 40 5,80 m 4,43 d 4,28 d 6,76 s 3,98 dd 6,93 s 2 JPtH 70 JPtH 60 JPtH 60 JPtH 40 5,77 m 4,40 d 4,24 d 6,76 s 3,58 dd 6,92 s 2 JPtH 70 JPtH 60 JPtH 60 JPtH 40 3,67 m 3,43 d 2,37 d 6,29 s 3,58 dd 6,60 s 2 JPtH 70 JPtH 60 JPtH 60 JPtH 40 * solvent: (a): acetone-d6; (b): methanol-d4; (c): chloroform-d1 12 b) a) Fig 3.23 Structures of (a) and (b) were determined by XRD a) b) c) Fig 3.24 Structures of 10 (a), 11 (b) and 13 (c) were determined by XRD Table 3.8 Some bond length of complexes 7, 9−11 and 13 (Å) O OR O O OR Pt 10 N (7, 9) Data anti-2 10 11 13 Pt−C5 Pt−N N2 Pt 10 N1 Cl (10, 11, 13) Pt−C9 Pt−C10 Pt−O Pt−Cl 2,4773(7) 1,993(3) 2,108(3) 2,141(3) 2,3527(7) 1,997(3) 2,199(3) 2,136(4) 2,110(4) 2,008(2) 1,999(3) 2,212(3) 2,140(3) 2,128(3) 2,038(2) 2,142(4) 2,005(5) 2,105(6) 2,078(5) 2,5086(13) 2,148(4) 2,133(3) 2,008(3) 2,081(3) 2,091(3) 2,5277(8) 2,152(3) 2,206(3) 2,010(3) 2,070(4) 2,056(4) 2,4268(9) 2,212(3) C9−C10 1,393(5) 1,388(5) 1,400(5) 1,436(8) 1,422(5) 1,450(5) XRD results show that the length of the Pt−Cl bond in 10 and 11 (Table 3.8) is consistent with the assumption that this bond is splitted in aqueous solution to dissociate into two ions as well as their molecular electrical conductivity 3.3 STUDY ON THE INTERACTION OF [Pt(μ-Cl)(iPrEug)]2 WITH PHOSPHINE AND DETERMINATION OF COMPONENT AND STRUCTURE OF OBTAINED COMPLEXES 3.3.1 Study on the interaction of [Pt(μ-Cl)(iPrEug)]2 with phosphine 13 When complex reacts with PR3 (R: phenyl, cyclohexyl), PR3 not only splits the Pt–Cl bond, but also cuts the Pt–(C=C) bond depending on the ratio of the participants Experimental results show that the reaction between and phosphine derivatives occurs according to the diagram in Fig 3.25 Through the purification process, we have obtained clean complexes 14–16 with efficiency 90–93% OCH2COOCH(CH3)2 H3CO 2PR3 OCH2COOCH(CH3)2 H3CO 2PR3 PR3 PR3 Pt Pt R3P Cl Cl Fig 3.25 Reaction between with derivatives of phosphine 3.3.2 Determination of the component and structure of obtained complexes The components and structure of 14–16 were determined by spectroscopic methods ESI-MS, IR, NMR and XRD (with 14 and 16) The results showed that the obtained complexes have structure as described in Fig 3.34 Tables 3.10 and 3.11 give some data on NMR and XRD of 14–16 Table 3.10 Some NMR signals of iPrEug in and 14–16, (ppm), J (Hz) Complex H8a H8b H9 H10cis 2,59/2,57 3,74-3,79 5,09 4,00 3,74 d 6,24 m 4,63/4,60 14 3,87 dd JPtH 100 JPtH 65 d 2JPtH 50 15 3,90 d 5,94 m 5,16 d 16 2,99 d 4,99 m 4,67 d C8 C9 38,2 91,2 14 41,1 121,83/121,75 H10trans 4,29/4,27 4,24/4,23 d JPtH 60 5,18 d 4,64 d C10 64,2 84,67/84,53 H3 6,57 H6 6,39 6,72 s 6,67 s JPtH 50 6,55 s 7,00 s 3JPtH 70 5,84 s 6,3 s 3JPtH 65 C5 141,1 129,45/129,4 Table 3.11 Values of some bond length (Å) and bond angle (0) of complexes 14 and 16 O O O O 10 Pt Cy3P (14) Data 14 16 14 16 10 O O Cl Pt−C5 Pt−Cl Pt−P 2,033(11) 2,4773(7) 2,3527(7) 2,3059(7) 2,026(2) 2,3968(7) 2,3097(7) Cl−Pt−C5 Cl−Pt−P Cl−Pt−C9 168,1(3) 92,77(10) 87,4(4) 177,95(6) 91,88(2) 86,86(2) O O Ph3P PPh3 Pt (16) Cl Pt−C9 2,230(11) Pt−C10 2,208(11) C9−C10 1,356(16) - - 1,299(3) C5−Pt−P P1−Pt−P2 C2C3PtP1 98,7(3) 89,46(6) 174,036(18) 93,50(15) 91,65(2) 14 a) b) Fig 3.34 Molecular models of 14 (a) and 16 (b) were determined by XRD 3.4 STUDY ON THE INTERACTION BETWEEN [Pt(μ-Cl)(iPrEug)]2 WITH AZOLIUM CHLORIDE SALTS 3.4.1 Study on the interaction between [Pt(μ-Cl)(iPrEug)]2 with azolium chloride salts Complexes 17–22 containing iPrEug and NHC were synthesized by the reaction of azolium chloride salt with complex in the presence of Ag2O or Na2CO3 with the yield of 85–90% The reaction happened according to the diagram in Fig 3.35 Complexes 20 and 21 were synthesized by the reaction of 18 with LiBr or KI according to the equation in Fig 3.35 with 95% efficiency Ph Ph N N N N N N N N N Ph Ph Bn2-imy 2NHC·HCl acetone Ph Bn2-bimy H3CO Ph Ph i Bn2-tazy OR H3CO Cl (NHC·H) Pr,Bn-bimy OR Ag2O/Na2CO3 NHC acetone Pt Pt Cl Cl Fig 3.35 Reaction diagram of with azolium salts with the presence of base O O O O O Ph LiBr/KI N Cl O Ph acetone/H2O 80 °C N Pt O O Ph [PtCl(iPrEug)(Bn2-bimy)] (18) 21: X = Br 22: X = I N N Pt X Ph [PtX(iPrEug)(Bn2-bimy)] (21, 22) Fig 3.36 Synthesizing reaction of 21 and 22 3.4.2 Determination of the component and structure of obtained complexes 15 From analysis results of elemental analysis, ESI-MS, IR, one-dimensional and two-dimensional NMR spectra, the structure of 17–22 is determined, in which iPrEug coordinates with Pt(II) through the C=C bond and the carbon atom of the benzene ring, the NHC ligand is at the trans position compared to the C=C bond (Fig 3.44) In particular, 17−22 are a very rare case of Pt(II) complexes containing three carbon complexing centers: aryl anion, neutral NHC and η2-olefin In addition, the rotational symmetry in solution of complexes 19 and 20 (Fig 3.39) is discovered due to the asymmetric NHC Tables 3.13–3.16 gives some data on MS, NMR and XRD spectra of 17–22 Table 3.13 Results of +MS spectra of 17–22, m/z (au), intensity (%) Complex i [PtCl( PrEug)(Bn2-imy)] (17) [PtCl(iPrEug)(Bn2-bimy)] (18) [PtCl(iPrEug)(Bn2-tazy)] (19) [PtCl(iPrEug)(iPr,Bn-bimy)] (20) [PtBr(iPrEug)(Bn2-bimy)] (21) [PtI(iPrEug)(Bn2-bimy)] (22) Ph R Cl (19a) R R' N Pt 10 N N Pt 10 Ph [M + Na]+ 765 (8) 815 (24) 765 (88) 766 (24) 858 (30) 906 (62) Ph R N N R' [M – X]+ 706 (100) 756 (100) 707 (100) 708 (100) 756 (100) 756 (100) (19b) Cl N R' N R' N N Pt Ph Ph R Cl (20a) N Pt Cl Ph (20b) Fig 3.39 Two rotational symmetries of complexes 19 and 20 Table 3.14.1H NMR signals of iPrEug in and 17–22a, (ppm), J (Hz) Complex H8a 2,59/2,57 3,05 d 17 JPtH 90 3,11 d 18 JPtH 90 3,10 d 19a JPtH 90 3,10 d 19b JPtH 90 3,09 d 20ab JPtH 90 3,14 d 20bb JPtH 90 3,13 d 21 JPtH 90 3,14 d 22 JPtH 90 * H8b H9 H10trans H10cis 3,74-3,79 5,09 4,00 4,29/4,27 3,75-3,68 5,79 m 4,52 d 4,82 d 2 ov JPtH 65 JPtH 60 JPtH 50 5,92 m 4,67 d 4,95 d 3,75 dd JPtH 65 2JPtH 60 2JPtH 50 5,92 m 4,58 d 4,90 d 3,82 dd 2 JPtH 65 JPtH 60 JPtH 50 5,85 m 4,62 d 4,88 d 3,82 dd JPtH 65 2JPtH 60 2JPtH 50 3,78-3,74 5,98 m 4,72 d 5,00 d 2 ov JPtH 65 JPtH 60 JPtH 50 5,98 m 4,70 d 4,99 d 3,86 dd 2 JPtH 65 JPtH 60 JPtH 50 5,93 m 4,73 d 5,05 d 3,74 dd JPtH 65 2JPtH 60 2JPtH 50 5,98 m 4,83 t-d 5,18 d 3,73 dd 2 JPtH 65 JPtH 60 JPtH 50 H3 6,57 6,70 s 6,72 s 6,73 s 6,73 s H6 6,39 5,57 s JPtH 65 5,78 s JPtH 65 5,37 s JPtH 65 5,45 s JPtH 65 6,64 s 6,65 s 6,74 s 6,78 s 6,08 s 5,66-5,63 ov 5,77 s JPtH 65 5,79 s JPtH 65 solvent: (a): acetone-d6; (b): chloroform-d1 Table 3.15 Some 13C NMR signals of and 17–22, ppm 16 Complex 17 18 19 20 21 22 C9 91,2 111,0 113,0 112,3 / 112,2 112,98 / 112,97 112,1 111,4 C10 64,2 84,1 86,4 85,4 / 85,1 86,3 / 85,9 85,4 83,9 C5 141,1 127,7 127,8 127,7 / 127,3 125,9 / 125,2 129,9 135,0 CNHC 172,9 184,2 177,0 181,8 / 181,7 184,3 184,5 Fig 3.44 Molecular models of 18 and 20–22 were determined by XRD Table 3.16 Some values of bond length (Å) and bond angle (0) of complexes 18 and 20–22 O O O O Phức chất Pt−CNCN Pt−C5 Pt−X Pt−C9 Pt−C10 C9−C10 X−Pt−C5 X−Pt−CNCN C5−Pt−CNCN PtC2X/NHC PtC2X/alkene 18 (X = Cl) 2,000(5) 1,997(5) 2,409(1) 2,219(5) 2,205(6) 1,378(8) 176,1(2) 91,2(2) 92,5(2) 70,2(2) 81,8(3) 10 Pt NHC X 20 (X = Cl) 1,996(6) 2,011(6) 2,401(2) 2,223(6) 2,207(7) 1,36(1) 175,2(2) 90,0(2) 92,5(2) 68,9(2) 79,3(3) 21 (X = Br) 2,006(5) 2,012(5) 2,5316(6) 2,222(5) 2,205(6) 1,372(8) 176,5(1) 90,6(1) 92,7(2) 70,5(1) 81,5(3) 22 (X = I) 2,002(2) 2,010(2) 2,7020(2) 2,227(2) 2,212(2) 1,376(3) 172,96(5) 92,19(5) 91,33(8) 72,80(5) 86,1(1) 17 3.5 SOME RESULTS FROM COMPARING THE STRUCTURE AND PROPERTIES OF ALL RESEARCH COMPLEXES By the reactions of complex with a number of reagents, 20 complexes have been synthesized and classified into groups I – V as shown in Fig 3.45 Group I includes 3–5 (convention is the cis configuration, which is structurally similar to the complexes [PtCl(arylolefin)(amine)]; Group II: 14 and 17–22 (convention is the trans configuration); Group III: 6–9; Group IV: 10–13; Group V: 15, 16 H3CO OR OR H3CO OR H3CO L2 Cl L1 (I) N (II) OR PR3 Pt Pt Pt X L2: PCy3, NHC X: Cl, Br, I H3CO N O Pt Pt OR H3CO Cl (III) N (IV) R3P Cl (V) Fig 3.45 Structure of the researching complex groups 3.5.1 The relationship between the structure and spectral properties ESI-MS Complexes containing Pt−Cl bonds (except for group I) on +MS spectrum tend to form fragment ions corresponding to [M - Cl]+ cation NMR Spectrometry The results of structural studies of complexes 2–22 show that iPrEug can coordinate with Pt(II) in the following two ways: O Pt O 10 O O O (A) O O O 10 Pt (B) When coordinated with Pt(II) according to way A, the NMR signals of protons and carbon near the complexation center of iPrEug has the following characteristics: i) Protons H3 and H6 are singlets In the signal of H6 there is a satellite signal because of 195Pt split with 3JPtH = 40–65 Hz On the spectrum, no signal of the proton H5 is observed, and the 13C signal has a low intensity due to becoming a quaternary carbon ii) Two H8 protons are not equivalent giving two resonance spectra while in the resonant signal of H8a, the satellite signal caused by 195Pt splits with a very large spin-spin coupling constant of about 90–110 Hz iii) δ of H9, H10 tend to decrease compared to iPrEugH depending on the influence of other ligands in the coordination sphere and their spectra appeared